In tissue engineering applications, a scaffold containing an interconnected porous structure is often highly desirable since these interconnected pores allow nutrients and signaling molecules to reach all of the cultured cells. In this study, microcellular injection molding, a mass production method for foamed plastic components, was combined with chemical foaming and particulate leaching methods to fabricate an interconnected porous structure using poly(-caprolactone) (PCL). Sodium bicarbonate (SB) was employed as the chemical foaming agent while carbon dioxide (CO2) was used as the physical foaming (blowing) agent. The results showed that interconnected porous structures of PCL, which depend on the composition of the materials used, could be successfully produced. Sodium bicarbonate not only generated CO2 to supplement the supercritical fluid microcellular injection molding, but also served as the nuclei for heterogeneous cell nucleation. Sodium bicarbonate and its byproduct, sodium carbonate, were also the porogens in the particulate leaching process, which further enhanced the porosity and interconnectivity. The morphologies and mechanical properties of the samples with different material compositions and porosities were discussed. The results of cell viability assays of 3T3 fibroblasts suggested that the resulting interconnected porous PCL scaffolds exhibited good biocompatibility. Cell spreading was affected by the porosity of the scaffold because of the physical restriction effect on the cell migration. Highly improved interconnectivity of the scaffold provided more space for the cells to spread.
Spherical foamable particles were synthesized by suspension polymerization of methyl methacrylate and styrene in the presence of a blowing agent. When the surrounding temperature was high enough to vaporize the blowing agent and soften the polymer shell, the particles were expanded due to pressure difference across the shell. The effects of initiator and crosslinker concentration on the particle size, average molecular weight, and molecular weight distribution of synthesized copolymer, pentane content and expansion properties (density, residual pentane, and dimensional stability of pre-expanded beads) of expandable particles were investigated. The results showed that the expansion behavior of the particles was dependent on molecular weight of the matrix polymer and size of the synthesized particles. In a constant copolymer molecular weight, the pre-expanded bead density decreased with increasing of particle size whereas it increased with molecular weight in a constant particle size. Moreover, the crosslinker improved dimensional stability of the pre-expanded beads.
In this study, different blends based on polylactic acid (PLA)/polyolefin elastomer (POE) and compatibilized PLA/POE was prepared by melt mixing. The compatibilizer glycidyl methacrylate-grafted-polyolefin elastomer (POE-g-GMA) was synthesized in a separate process. The Fourier transform infrared spectrum confirmed the reaction of POE and glycidyl methacrylate. Meanwhile, the morphology of dispersed phase was observed by scanning electron microscope. The results indicated that the compatibilizer has improved the compatibility and interfacial adhesion between PLA and POE phase. The rheological test results revealed that the introduction of compatibilizer could enhance the storage modulus and melt complex viscosity of PLA/POE blends. The foamability was studied in the presence of azodicarbonamide as a chemical blowing agent in the batch foaming process. Morphology of foams such as porous cell size, porous cell population density, and foam density were studied. It was found that the presence of POE in PLA foams has a great influence on their mechanical properties and the toughness. Addition of POE-g-GMA in samples increased elastic modulus of foams and decreased their strain at break.
Mixed matrix membranes made from silica nanoparticles and microcellular polymers were prepared from Matrimid® 5218 combined with tetramethoxysilane, tetraethoxysilane, and tetrapropoxysilane via the sol–gel method. The nanoparticles were prepared in situ during membrane casting yielding a homogeneous distribution inside a foamed polyimide structure. Mixed matrix membranes with SiO2 contents up to 16% wt. were treated at 60℃, 100℃, 150℃, and 200℃. Thermal gravimetric analysis and Fourier transform infrared spectroscopy analyses were performed providing information on chemical composition and thermal stability, while the porous structure (average cell diameter and cell density) was studied by scanning electron micrograph. Also, dynamic mechanical analysis was used to determine the glass transition temperature (Tg) and elastic modulus. Finally, the gas transport properties were studied in terms of treatment temperature, feed pressure, SiO2 loading, and testing temperature. CO2 permeability was found to increase by a factor of 3–4 at 3% SiO2 content using tetraethoxysilane in Matrimid, while ideal selectivity for CO2/CH4 separation was constant. Finally, the plasticization effect was practically eliminated by the introduction of SiO2 nanoparticles.
The semicrystalline character of low density polyethylene adds severe difficulties to its foamability by a batch process in which the gas is dissolved into the polymer matrix under subcritical conditions. To improve the low density polyethylene foamability, two strategies have been used: the addition of nanoclays and a partial crosslinking of the polymer matrix. On the one hand, the use of nanoparticles is suggested because they act as heterogeneous nucleating sites reducing the cell size and increasing the cell density. On the other hand, crosslinking is also adopted as a solution because both the crystallinity (and hence, the gas solubility and diffusivity) and the extensional rheological properties of the polymer matrix are highly influenced by the crosslinking degree achieved. Results indicate that despite the fact that the presence of nanoclays deteriorates the rheological behaviour of the nanocomposites and, hence, the later foaming behaviour, the use of partially crosslinked polymer matrices allows achieving high expansion ratios (around 7.5) as well as enhanced cellular structures with cell sizes of approximately 15 µm.
Obtaining high-density polyethylene-based microcellular foams is a topic of interest due to the synergistic properties that can be obtained by the fact of achieving a microcellular structure using a polymer with a high number of interesting properties. However, due to the high crystallinity of this polymer, the production of low-density microcellular foams, by a physical foaming process, is not a simple task. In this work, the proposed solution to produce these materials is based on using crosslinked high-density polyethylenes. By crosslinking the polymer matrix, it is possible to increase the amount of gas available for foaming and also to improve the extensional rheological properties. In addition, the foaming time and the foaming temperature have also been modified with the aim of analyzing and understanding the mechanisms taking place during the foaming process to finally obtain cellular materials with low densities and improved cellular structures. The results indicate that cellular materials with relative densities of 0.37 and with cell sizes of approximately 2 µm can be produced from crosslinked high-density polyethylene using the appropriate crosslinking degree and foaming parameters.
A temperature-rising batch foaming process with supercritical carbon dioxide (ScCO2) as blowing agent was used to prepare epoxy resin foams consisting of diglycidyl ether of bisphenol A and m-xylylenediamine. The dissolution and diffusion behaviors of CO2 in pre-cured epoxy resin were investigated, as well as the parameter effect of CO2 saturation step and foaming step on the cell characteristics. It was proved that closed-cells could be generated for CO2 unsaturated samples and the cell characteristics with the same dissolved CO2 concentration were similar. The merged and cracked bubble morphologies were usually obtained for CO2-saturated epoxy resin samples. With increasing CO2 concentration from 0.021 g CO2/g epoxy resin to 0.061 g CO2/g epoxy resin in the unsaturated samples, the cell size increased from 170.2 µm to 262.6 µm and the cell density decreased from 6.8 x 105/cm3 to 3.1 x 105/cm3. Bubble nucleation and growth occurred simultaneously with curing reaction in temperature-rising step. As the final foaming temperature increased from 60℃ to 120℃, the cell size of samples with dissolved CO2 concentration of 0.021 g CO2/g epoxy resin increased from 172.7 µm to 369.0 µm, while the cell density first increased from 6.8 to 7.3 and then decreased to 3.5. The cell size of samples with CO2 concentration of 0.031 g CO2/g epoxy resin increased from 145.3 µm to 180.5 µm with foaming time from 5 min to 20 min, but changed slightly when curing reaction almost finished and CO2 was depleted after 20 min.
The Young’s modulus and shear modulus of extruded polystyrene foam were obtained by measurements using the longitudinal and flexural vibration methods on specimens with various lengths and performing a subsequent numerical analysis on the test data. In addition to the vibration tests, ISO 844 compression and ASTM C273/C273M-11 shear tests were conducted, and the results were compared with those obtained from the vibration tests. The Young’s modulus values could be measured accurately by the longitudinal and flexural vibration tests while reducing the effects of the specimen configuration. In contrast, the shear modulus value was often dependent on the specimen configuration. The Young’s modulus and shear modulus values obtained from the vibration tests were often higher than those obtained from the standardised tests because the bending of cell wall is not induced in the vibration test. Although a provisional method for reducing the influence of the specimen configuration was proposed based on the numerical results, further research is required to measure the elastic modulus of extruded polystyrene foam accurately.
Studies about polypropylene nanocomposite foams are receiving attention because nanoparticles can change physical and mechanical properties, as well as improve foaming behavior in terms of homogeneous cell structure, cell density, and void fraction. In this research, the foaming behavior of polypropylene, polypropylene/long-chain branched polypropylene (LCBPP) 100/20 blend, and polypropylene/LCBPP/halloysite nanocomposites with 0.5 and 3 parts per hundred of resin (phr) is studied. The LCBPP was used to improve the rheological properties of polypropylene/LCBPP blend, namely the degree of strain-hardening. Transmission electron microscopy observation indicated that halloysite nanotube particles are well distributed in the matrix by aggregates. Subsequent foaming experiments were conducted using chemical blowing agent in injection-molding processing. Polypropylene foam exhibited high cell density and cell size as well as a collapsing effect, whereas the polypropylene/LCBPP blend showed a reduction of the void fraction and cell density compared to expanded polypropylene. Also, the blend showed reduction of the collapsing effect and increase of homogeneous cell size distribution. The introduction of a small amount of halloysite nanotube in the polypropylene/LCBPP blend improved the foaming behavior of the polypropylene, with a uniform cell structure distribution in the resultant foams. In addition, the cell density of the composite sample was higher than the polypropylene/LCBPP sample, having increased 82% and 136% for 0.5 and 3 phr of loaded halloysite nanotube, respectively. Furthermore, the presence of halloysite nanotube increased crystallization temperature (Tc) and slightly increased dynamic-mechanical properties measured by dynamic-mechanical thermal analysis. By increasing halloysite nanotube content to 3 phr, the insulating effect increased by 13% compared to polypropylene/LCBPP blend. For comparative purposes, the effect on foaming behavior of polypropylene/LCBPP was also investigated using talc microparticles.
The impregnation of carbon nanotubes within fiber-reinforced polymers (FRPs) is a sought after capability for the advancement of composite systems. This study evaluates the novel processing of a carbon nanotube nanocomposite that has been developed to incorporate varying carbon nanotube loadings within final composite foams. This material is manufactured through a melt mix process of carbon nanotubes and polystyrene at ~2.0–13.0 wt.% that further underwent a plasticization process in an acetone solvent. The chemical foaming agent 2.2'-Azobi(isobutyronitrile) is used to facilitate foaming at a constant 3.0 wt.% concentration. The foamed nanocomposite results in a carbon nanotube-loaded micro-porous structure showing capabilities of delivering localized carbon nanotube placement within fiber composite laminate systems. This report’s aim is to illustrate the effects of plasticizing polystyrene-carbon nanotube nanocomposite and calendaring the softened material to form foams imbedded with carbon nanotubes (carbon nanotubes). Scanning electron microscopy, differential scanning calorimetry, thermogravimetric analysis, and Fourier transform infrared spectroscopy were the tools that are used to characterize the materials at the various morphologies with their findings inclusive.
Wood plastic composites have gained relevance in recent years as an alternative to wood boards. However, because the cavities in wood fibres are compressed by high processing pressure during the extrusion of wood plastic composites, the product densities show a range of up to 1.5 g/cm3 depending on wood content and base material. Particularly in large-sized products, this may be disadvantageous for processors and end users. Foaming of the plastic matrix is a promising approach to reduce the density of wood plastic composites products. This article discusses the foam extrusion of PP-based wood plastic composites with chemical blowing agents in combination with the Celuka technique. Integral wood plastic composites foam with a rigid and plain outer layer was produced using a parallel, counter rotating twin screw extruder. The profiles obtained were analysed with respect to foam structure and mechanical properties. It was possible to achieve a density reduction of up to 0.7 g/cm3 in the foamed wood plastic composites profiles. Furthermore, we demonstrate that wood fibre length and type of chemical blowing agent have a strong effect on the resulting foam morphology.
It is critical to broaden the applications of poly(L-lactic acid) foams by improving heat resistance properties. The stereocomplex crystallites that are formed by melt blending of poly(L-lactic acid)/polylactide possess high melting point of about 220℃ and thus exhibit high heat resistance; therefore, the introduction of stereocomplex crystallites tends to improve the thermal stability of poly(lactic acid) foam. Unfortunately, using the solid-state foaming method, it was found that the expansion ratio of the obtained poly(lactic acid) foams was compromised with the value of 1.7 times once the stereocomplex crystallites were formed during the sample saturation stage. In this study, by applying a high compression molding temperature of 230℃, the as-prepared poly(L-lactic acid) and poly(L-lactic acid)/polylactide blends were amorphous. After being CO2 saturated at a mild condition, the specimens were foamed at 90–160℃. The wide-angle X-ray diffraction profiles presented that the stereocomplex crystallites and PLA homocrystals were in-situ generated during the foaming process. It is observed that the in-situ formed stereocomplex crystallites could act as the physical cross-linking agent to stabilize the nucleated bubbles and suppress cell coalescence, resulting in the increased expansion ratio (with value of about 23.6–25.6 times) and cell density, especially at high foaming temperatures and extended foaming time. Furthermore, the in-situ formed stereocomplex crystallites during the foaming increased the heat resistance performance of poly(L-lactic acid) foams. This novel crystallization control method helps us to find a balance point in preparing poly(L-lactic acid) foam with high expansion ratio, well-defined cell structure and high heat resistance performance.
Foam injection molding is a processing technology particularly interesting for biodegradable polymers, which present a very narrow processing window, with the suitable processing temperatures close to the degradation conditions. The addition of a physical blowing agent, besides decreasing the final part weight, reduces both the viscosity and the glass transition temperature of the polymer melt, allowing the processability of these materials at lower temperatures. In this work, structural foams of polylactic acid with nitrogen as physical blowing agent were obtained by foam injection molding. In particular, the effects of back pressure, namely the pressure imposed inside of the cylinder when the screw is returning back to prepare a new amount of material to be injected, and of the injection flow rate on foaming and mechanical properties of the molded parts was assessed. It was found that the samples molded adopting a higher injection flow rate are shorter than those injected at lower flow rate, and this result was ascribed to the large compressibility of the injected shot. As far as the mechanical properties of the foamed parts, it was found that the modulus decreases with decreasing density. However, the density reduction is not the only significant parameter, but also the morphology of the foams should be taken into account in order to justify the differences between tensile and flexural modulus.
New polyols with isocyanuric structure were synthesized by thiol-ene "click" chemistry of triallyl isocyanurate with 1-thioglycerol and 2-mercaptoethanol. The synthesized polyols, prepared with high reaction rates and in very high yields, were chemically and structurally characterized. These polyols were used for the preparation of rigid polyurethane foams with excellent physical–mechanical properties and inherent flame retardancy. By alkoxylation of isocyanuric polyols with propylene oxide and/or ethylene oxide in a self-catalytic process, odorless polyols with lower hydroxyl numbers and lower viscosities were obtained, leading to PU foams with good properties, but without inherent flame retardancy. The synthesized polyols with isocyanuric structure are suitable for the preparation of all types of rigid polyurethane foams, including thermoinsulation of freezers, buildings, storage tanks and pipes for the food and chemical industry, for packaging, and as wood substitutes.
Microcellular polystyrene foam sheets prepared by extrusion foaming with CO2 as the blowing agent were found to exhibit a significant anisotropy in mechanical behavior which could not be explained solely by the shape anisotropy of the cells and/or the preferential orientation of polystyrene molecules in the machine direction. Surprisingly, samples allowed to fully relax were still found to maintain part of their mechanical anisotropy, which was attributed to the weakness of the cell walls perpendicular to machine direction.
Representative volume elements of random equilateral Kelvin open-cell microstructures were modeled for the open-cell foam. We adopted the periodic boundary conditions developed in our previous research. The quasistatic compression properties of the representative volume elements in random Kelvin open-cell aluminum foam samples, both with different relative densities and different cross-sections of the beams in the structures were investigated. The results show that the features of the stress–strain curves in the representative volume elements with different relative densities and different cross-sections were similar, and the relationships between the yield strengths and relative densities of representative volume elements with four different cross-sections all agreed well with the quadratic power function. Among the representative volume elements with four different cross-sections, the yield strengths of the representative volume elements with a Plateau border cross-section were significantly larger than in representative volume elements with other cross-sections, while the yield strengths of representative volume elements with circular cross-sections were smaller than in representative volume elements with other cross-sections. This indicates that the simulation results of the compression strengths for open-cell foam in which the representative volume elements with circular cross-sections were employed are significantly smaller than their actual values. The main reason for this is that the moments of inertia in the Plateau border cross-sections are significantly greater than in the circular cross-sections of the same area. Our investigation results revealed that the compression responses of the representative volume elements for random equilateral Kelvin open-cell microstructures demonstrate isotropic behavior on the xoy plane, the yoz plane, and the xoz plane.
Expanded polyvinyl alcohol is regarded as excellent buffering and leak-proof packaging material of liquid products due to its characteristics such as good liquid absorption and liquid retention properties, good mechanical properties under dry condition, and good rebound resilience under wet condition. Through static compression experiment, this study analyzed the mechanical properties and energy absorption properties of expanded polyvinyl alcohol with different densities under different temperatures and relative humidity. The experimental results showed that the effect of ambient temperature and humidity on expanded polyvinyl alcohol performance was mainly to change its internal moisture. The initial elastic modulus, plateau stress, and energy absorption value per unit volume of expanded polyvinyl alcohol increased as the density increased, the relative humidity decreased, or temperature increased. The above research can provide reference for applications of expanded polyvinyl alcohol on buffering packaging in actual logistic environment.
In this research, polyols from rapeseed oil and recycled poly(ethylene terephthalate) were synthesized by two-step continuous synthesis with a different rapeseed oil and poly(ethylene terephthalate) concentration. All rapeseed oil/poly(ethylene terephthalate) polyols showed complete compatibility with blowing agent Solkane 365/227. The resulting polyols were used to prepare rigid polyurethane foams which were characterized with various techniques for determination of their physical, mechanical and thermal insulation properties. The effect of rapeseed oil and poly(ethylene terephthalate) concentrations in polyols on the characteristics of rigid polyurethane foams was investigated. The results showed that obtained rigid polyurethane foams were suitable for thermal insulation appliance. Also, the potential use of rapeseed oil as raw material combined with poly(ethylene terephthalate) to synthesize polyols with good compatibility with blowing agent was confirmed.
Novel isophorone diisocyanate-based flexible polyurethane foams were prepared by the one-step method in a computerized foam qualification system (FOAMAT). The experimental conditions to obtain this type of foams, in relation to the nature and concentration of catalysts as well as the reaction temperature, were established as no data were available in scientific literature. The chemical reactions occurring during the foam generation process were monitored in situ by attenuated total reflectance-FTIR spectroscopy. The kinetics of the foam generation was fitted to an nth order model and the data showed that the foaming process adjusted to a first-order kinetics. The physical changes as pressure, foam height, and dielectric polarization were monitored by the FOAM software (FOAMAT). According to these parameters, the foaming process was divided into four steps: bubble growth, bubble packing, cell opening, and final curing.
Wood is the main industrial source for obtaining cellulose. It is a natural composite, constituted by cellulose, polyoses, lignin, small amounts of extracts and mineral salts, wherein cellulose is the most abundant component. Many studies are being developed for obtaining materials based on natural fibers, which combine interesting properties such as renewability, biodegradability, low density and low cost. Aerogels are solid, lightweight materials with high porosity and high internal surface area. These features combined in one single material make the aerogels a differentiated product with potential for use as an adsorbent. In this context, aerogels made of cellulose nanofibers obtained from short-fiber cellulose of Eucalyptus sp. were made. The cellulose suspension was first disintegrated by a mechanical grinder, and the aerogels were undergone to freeze-drying. The characterization of the samples was performed by apparent density, porosity, scanning electron microscopy, Fourier transform infrared spectroscopy and thermogravimetric analyses. According to the micrographs obtained by scanning electron microscopy and field emission gun scanning electron microscopy, it was observed the formation of pores formed by the interconnection of cellulose fibers. The apparent density of the starting cellulose fibers (pressed plates) was 0.6998 g.cm–3 and the aerogel density decreased to 0.0240 g.cm–3. The values for aerogel porosity were about 97%, which benefits the passage of liquids and gases from the external environment to the internal structure of the material. Fourier transform infrared spectroscopy and thermogravimetric analyses showed no change in the chemical composition or in the thermal stability of the obtained aerogels in comparison to their starting materials.
The micro-structure and mechanical properties of lightweight porous foams synthesized by dispersing expanded perlite particles (expanded siliceous volcanic glass) in a matrix of epoxy resin were examined. Foams were fabricated with three distinct particle size ranges and, within each size, samples covered a density range of 0.15–0.45 g/cm3. The effects of particle size variation on compressive strength, effective elastic modulus, and modulus of toughness were investigated. An upper and a lower bound were estimated for the elastic modulus of particles in EP/epoxy foams. EP/epoxy foams showed Reuss-like behaviour similar to metals but atypical of non-plastic materials. In addition, results illustrated the significant contribution of the expanded perlite particles in the effective elastic modulus of the foams. Micro-structure of expanded perlite particles was examined and related to their macroscopic properties via two geometrical relationships. Post-test microscopic observations coupled with macroscopic observations taken during the test were used to understand the effect of particle size on the behaviour of the foams under compressive load. Observations revealed the presence of three different failure modes for all foams regardless of their particle size and density; however, the strain to activate each mode was different for each foam type.
In this work, injection molding was used to produce polylactic acid foams using azodicarbonamide as a chemical foaming agent and to study the effect of wood flour concentration (15, 25, and 40% wt.) on morphology (scanning electron microscopy), density (gas pycnometry), as well as mechanical (tensile, flexural, and impact) and thermal (differential scanning calorimetry) properties. In particular, density reduction was controlled by the amount of material injected (shot size). The results showed that polylactic acid properties increased with wood content, but decreased with density reduction. Nevertheless, specific flexural modulus (per unit weight) always increased with foaming. Foaming was also shown to significantly increase polylactic acid crystallinity.
Thermoplastic polyurethane is one of the most versatile thermoplastic materials being used in a myriad of industrial and commercial applications. Thermoplastic polyurethane foams are finding new applications in various industries including furniture, automotive, sportswear, and packaging because of their easy processability and desirable, customizable properties. Low bulk density and a good foam microstructure are important properties that affect the mechanical properties, economics, and performance of the final product. In this study, the effect of a cross-linking agent on the foamability of microcellular injection molded thermoplastic polyurethane was studied with an aim to reduce the bulk density while achieving a consistent microstructure. Gel permeation chromatography showed an increase in the weight average molecular weight by 5.0% with the addition of a cross-linking agent. Rheological studies on the materials showed that the addition of a cross-linking agent increased the storage modulus and viscosity, while reducing the tan value. Using microcellular injection molding, cross-linked thermoplastic polyurethane could be foamed to a minimum density of 0.159 g/cc at the higher end of the processing window, as compared with a minimum density of 0.193 g/cc for pure thermoplastic polyurethane foam. Scanning electron microscope analyses of the foamed parts showed a bimodal foam structure for thermoplastic polyurethane with a cross-linking agent and a more integral foam structure with less cell coalescence even at higher density reductions.
A novel type of economical lightweight foam with density from 0.15 to 0.45 g/cm3 was made from a high volume fraction of expanded volcanic glass (perlite) in an epoxy matrix. The compressive strength, effective elastic modulus, and modulus of toughness of the foams all increased with the foam density. The strength increased linearly, peaking at 1.7 MPa whereas the effective elastic modulus and modulus of toughness increased at parabolically increasing and decreasing rates, respectively. The specific compressive stress of the newly developed foam in the density range of 0.3–0.44 g/cm3 is comparable with foams made from alumina, aluminium–silicon carbide, closed cell phenolic resin, and closed cell polypropylene. Post-test SEM observations coupled with photogrammetry during the tests revealed three different failure modes: longitudinal splitting, shear failure, and compression failure were present over the whole density range. The material was found to be a good candidate for the stiffening cores within sandwich panels.
Styrene–ethylene–butylene–styrene and its blends containing 10, 30 and 50 wt% polystyrene were subjected to batch foaming using physical blowing agent carbon dioxide. At higher foaming temperatures (80–110℃), complex viscosity (*) and storage modulus (E') were found to control the volume expansion ratio and the shrinkage of foams. For a given composition, optimal volume expansion was achieved at temperatures close to the glass transition temperature (T g ) of the polystyrene phase of that composition, indicating the presence of a complex viscosity window favourable for the foaming process. Blends with 30% and 50% polystyrene content possessed higher values of E' and *, and produced stable foams having higher volume expansion ratio, when foamed within their respective * windows. At a much lower foaming temperature (35℃), polystyrene was found to have a nucleating effect. However, irrespective of rheological properties, all foams showed prominent shrinkage. A higher polystyrene content resulted in a lower volume expansion ratio, as well as shrinkage over a shorter period of time and a greater extent of shrinkage in the same time span. This can be attributed to the selective foaming of the ethylene–butylene phase, hindered by the stiff polystyrene aggregates.
In this work, styrene–methyl methacrylate copolymer particles were synthesized by suspension polymerization process with different copolymer compositions. A system was designed to measure the solubility and diffusivity of n-pentane in the synthesized copolymers. The designed system consisted of the self-sealing cell equipped to the pressure and temperature controllers. The synthesized copolymer particles were impregnated by n-pentane and their expansion were recorded visually. Furthermore, the solubility and diffusivity of n-pentane in copolymer particles were measured by the same apparatus. The effect of different foaming conditions on the solubility and diffusivity of n-pentane in the samples were examined. It was concluded that the sorption pressure and temperature have contradictory effects on the solubility and diffusivity of n-pentane in styrene–methyl methacrylate copolymers at different sorption pressures. It was concluded that with methyl methacrylate content increment in copolymer, the diffusivity and dissolved n-pentane content in copolymer were reduced.
Thermoplastic polyurethane is one of the most versatile thermoplastic materials being used in a myriad of industrial and commercial applications. Thermoplastic polyurethane foams are finding new applications in various industries including the furniture, automotive, sportswear, and packaging industries because of their easy processability and desirable customizable properties. In this study, three methods of manufacturing injection molded low density foams were investigated and compared: (1) using chemical blowing agents, (2) using microcellular injection molding with N2 as the blowing agent, and (3) using a combination of supercritical gas-laden pellets injection molding foaming technology and microcellular injection molding processes using co-blowing agents CO2 and N2. Thermal, rheological, microscopic imaging, and mechanical testing were carried out on the molded samples with increasing amounts of blowing agents. The results showed that the use of physical blowing agents yielded softer foams, while the use of CO2 and N2 as co-blowing agents helped to manufacture foams with lower bulk densities, better microstructures, and lower hysteresis loss ratios. Chemical blowing agent-foamed thermoplastic polyurethane showed an earlier onset of degradation. The average cell size decreased and the cell density increased with the use of co-blowing agents. A further increase in gas saturation levels showed a degradation of microstructure by cell coalescence.
The effect of azodicarbonamide as chemical blowing agent on the morphology, cure kinetics and physical properties of natural rubber foam is investigated. From the morphology, when the amount of chemical blowing agent increases from 3 to 4 phr, the bubble size in the rubber matrix slightly decreases due to the increase of vulcanization reaction rate from the presence of amine fragment species as by-products from the decomposition of azodicarbonamide. The coalescence between bubbles is observed in the specimen with 5 and 6 phr of azodicarbonamide owing to high gas content in the rubber matrix. Moreover, the scorch time slightly reduces and cure rate increases as a function of azodicarbonamide content. The autocatalytic model can be used to explain the curing reaction and mechanism of this natural rubber foam. Furthermore, the activation energy (Ea) directly relates to the bubble size and microvoid structure of natural rubber foam. When compared with the vulcanized natural rubber without adding chemical blowing agent, it is found that the bulk density of natural rubber foam significantly decreases and the volumetric expansion ratio of natural rubber foam increases at high content of chemical blowing agent. Moreover, natural rubber foam at 4 phr of azodicarbonamide exhibits the lowest thermal expansion coefficient due to the smallest bubble size with less coalescence.
Foams for biomedical applications were made from polyvinyl alcohol, polyvinyl alcohol / polyvinyl pyrrolidone blend and their nanocomposites with nanoclay by clean processes. Air was entrapped into the aqueous polymer solutions during vigorous mixing and then the solutions were freeze-dried. The foams structure was stabilized by crosslinking via gamma irradiation without using any harmful chemicals. The hydrophilic biocompatible foams possessed interconnected open cell structure with remarkable capacity to absorb and retain water. The foams in wet state were soft and flexible. Desirable pore structure and higher water absorption was obtained at a solution concentration of 5 wt% for both polyvinyl alcohol and polyvinyl alcohol / polyvinyl pyrrolidone foams and also for the nanocomposite foams. The polyvinyl alcohol / polyvinyl pyrrolidone foams at a composition of 80/20 had a uniform porous structure. Addition of 20 wt% polyvinyl pyrrolidone increased the size and interconnectivity of the cell structure and rendered more flexible foams than the neat polyvinyl alcohol. Also the nanoclay, in the nanocomposite foams, elevated pore population through generation of more air bubbles during aqueous polymer solution mixing.
A simple route has been adopted for the fabrication of polyurea using polycondensation of 4,4'-diphenylmethane diisocyanate and 1,4-phenylene diamine. Amalgamation of polystyrene, polyurea and functional graphene (F–G) yielded a series of nanocomposite foams. The morphological, electrical, mechanical, thermal, and flammability properties of materials were investigated and found to be dependent upon the intrinsic properties of graphene-based materials and their state of dispersion in matrix. Field emission scanning electron microscopy revealed a strong interaction between polystyrene/polyurea and functional graphene surface forming unique layered cellular structure. Mechanical results revealed a synergistic interaction between F–G and polystyrene/polyurea matrix providing a shielding mechanism against graphene layer damage during compression. The 10% thermal decomposition temperature of polystyrene/polyurea/F–G 1–5 foams measured was in the range of 432–470℃. UL 94 showed V-1 rating for polystyrene/polyurea foam, while polystyrene/polyurea/F–G 1–5 foams attained V-0 rating. Water absorption capacity was improved steadily with the time and was maximum after 96 h for polystyrene/polyurea/F–G 5 foam (4.53%). Functional graphene also produced excellent electrical conductivity improvement in polystyrene/polyurea/F–G 5 foam (101) relative to polystyrene/polyurea/F–G 1 foam (10–2) and neat polystyrene/polyurea foam materials (10–7).
Polystyrene/multi-wall carbon nanotube composite with an interconnected honeycomb-like structure was prepared by firstly coating the surface of the polystyrene pellets with multi-wall carbon nanotube, and sequentially welded through an ultrasound vibration technique. The mechanical and morphological properties of as-prepared composite were investigated in various measurements. It was found that an aggregative and honeycomb-like morphology of multi-wall carbon nanotube existed in the polystyrene/multi-wall carbon nanotube composite according to the polarized optical microscopic and scanning electron microscopic results; the ultrasound vibration could benefit to the performance of flexural strength. Furthermore, different composite foams were studied in this work, employing supercritical carbon dioxide as a blowing agent. Compared to other foams prepared by the conventional methods, the compressive strength of the foams derived from as-described novel method, was significantly improved. Also, being ascribed to this interconnected structure by coating carbon nanotube on polystyrene pellets, good electrical conductivity of 0.05–0.11 S/m was achieved in the novel composite foams.
Nanocomposite foams based on Nylon 6 and nanocrystalline cellulose were prepared via extrusion and injection molding to study the effect of nanocrystalline cellulose concentration (0 to 5%), chemical foaming agent content (0, 1%, and 2%), and mold temperature (30℃ and 80℃) on the morphological, physical, and mechanical properties of the samples. Nanocrystalline cellulose content, especially between 1 and 3 wt%, was very effective in reducing the cell size and increasing the cell density of the foam structure. Nanocrystalline cellulose addition (0–5%) was found to increase density (4% for composites and 20% for foams), tensile strength (10% for composite and 13% for foams), tensile modulus (20% for composites and 34% for foams), and flexural modulus (37% for composites and 29% for foams), but decreased the impact strength (35–40% for composites and 20–40% for foams). Foaming agent addition (1%) was able to improve the specific tensile (10%) and flexural (12%) moduli, tensile strength (14%), elongation at break (6%), and impact strength (27%). Finally, higher mold temperature decreased skin thickness and, consequently, decreased the mechanical properties, mostly tensile strength of the foam samples (1% for composites and 18% for foams).
The thermal conductivity and fire response of multiwall carbon nanotube/polyurethane foam composites are investigated for ~45 kg/m3 foams with multiwall carbon nanotube concentrations of 0.1, 1, and 2 wt.%. The thermal conductivity of such nanocomposites shows a modest increase with increased multiwall carbon nanotube content, which is explained by a high value of interfacial thermal resistance, as predicted by existent thermal models. A strong correlation between multiwall carbon nanotube content, foam’s cellular morphology, and fire behavior was observed. The flame propagation speed increases with the addition of 0.1 wt.% multiwall carbon nanotubes and then reduces as the multiwall carbon nanotube content increases. The mass lost after flame extinction reduces with the addition of multiwall carbon nanotubes, suggesting an increased resistance to flame attack due the multiwall carbon nanotube presence.
Stochastic foam models are generated from Voronoi spatial partitioning, using the centers of equi-sized hard spheres in random periodic distributions as seed points. Models with different levels of polydispersity are generated by varying the packing of the spheres. Subsequent relaxation is then performed with the Surface Evolver software which minimizes the surface area for better resemblance with real foam structures. The polydispersity of the Voronoi precursors is conserved when the models are converted into equilibrium models. The relation between the sphere packing fraction and the resulting degree of volumetric polydispersity is examined and the relations between the polydispersity and a number of associated morphology parameters are then investigated for both the Voronoi and the equilibrium models. Comparisons with data from real foams in the literature indicate that the used method is somewhat limited in terms of spread in cell volume but it provides a very controlled way of varying the foam morphology while keeping it periodic and truly stochastic. The study shows several strikingly consistent relations between the spread in cell volume and other geometric parameters, considering the stochastic nature of the models.
Recent changes in legislation have forced one-component foam producers to drop the amount of free monomeric isocyanate in their polyurethane systems. Also, it is required that commercial polyurethane aerosol cans exhibit at least one year of shelf life and polyurethane foams must be classified as B2 on the fire testing following DIN 4102. This paper reports on a systematic optimization study of polyurethane formulations dedicated to address these current industry requirements. A one-component foam system exhibiting simultaneously all of these parameters was achieved by reacting conventional diols, a relatively low-molecular weight monol (2-ethylhexanol), a flame retardant high-molecular weight monol (tris(bromoneopentyl)alcohol), a methylene diphenyl diisocyanate-based prepolymer (GreenAdduct 13), and a small amount of 2,4'-toluene diisocyanate. The use of monols allows producing prepolymers with low free methylene diphenyl diisocyanate by preventing chain extension and, therefore, avoiding extreme viscosity build-up. Toluene diisocyanate also promotes a lower viscosity inside the aerosol can, which enables the use of high enough quantities of high-molecular weight flame retardant monol to achieve a B2 fire test classification.
Structure–property behavior of the palm olein-based natural oil polyol (E-135 NOP) was investigated in viscoelastic "memory" foams. In a model viscoelastic foam formulation, the E-135 NOP with pendant hydroxyls was used as a drop-in replacement for the well-defined model polyether polyol with terminal hydroxyls, Poly-G® 76-120. Both polyols have comparable equivalent weight and concentrations of primary and secondary hydroxyls. The data showed that replacing Poly-G® 76-120 polyether polyol with the E-135 NOP did not significantly impact the foaming reactivity. Increasing the E-135 NOP concentration in the VE foams increased the average foam cell size while maintaining the open cell structure. Aging properties of the VE foams were mostly unaffected by the replacement of the Poly-G® 76-120 with the E-135 NOP. Furthermore, addition of E-135 had no impact on foam density; however, it increased the support factor of the viscoelastic foams. Differential scanning calorimetry, dynamic mechanical analyzer, and Fourier transform infrared spectroscopy analyses indicate less defined morphological separation of hard and soft segments in the viscoelastic foams with higher concentration of E-135 NOP. Overall, the results demonstrated the feasibility that natural oil polyols can be used in viscoelastic polyurethane foams to replace a significant portion of the polyether polyols with comparable equivalent weights and concentrations of primary and secondary hydroxyls. In future, the feasibility study of E-135 NOP as a drop-in replacement of combination polyether polyols in viscoelastic foams formulation will be conducted. Furthermore, the effect of palm olein-based natural oil polyol in high resilience foam will be evaluated.
In this research work, foaming behavior of selected polyethylene blends was studied in a solid-state batch process, using CO2 as the blowing agent. Special emphasis was paid towards finding a relationship between foamability and thermal and rheological properties of blends. Pure high-density polyethylene, linear low-density polyethylene, and their blends with two weight fraction levels of high-density polyethylene (10 and 25%wt.) were examined. The dry blended batches were mixed using an internal mixer in a molten state, and then the disk-shaped specimens, 1.8 mm in thickness, were produced for foaming purposes. The foaming step was conducted over a wide range of temperatures (120–170℃), and the overall expansion and cellular morphology were evaluated via density measurements and captured SEM micrographs, respectively. Three-dimensional structural images were also captured using a high resolution X-ray micro CT for different foamed samples and were compared. Rheological and DSC tests for the virgin and blends were also performed to seek for a possible correlation with the formability. Based on the results, blended polyethylene foams exhibited remarkable expansion and highly enhanced cell structure compared to pure polymers. Bulk density, as low as 0.33 g/cm3, was obtained for blends, while for the virgin high-density polyethylene and linear low-density polyethylene, bulk density lower than 0.5 g/cm3 was not attainable. The lowest density was observed at a foaming temperature of 10–20℃ above the melting (peak) temperature obtained via DSC test. Rheological characteristics, including storage modulus and cross-over frequency value, were also found to be the indicators for the materials foaming behavior. Moreover, blends with 25% wt. of high-density polyethylene exhibited the highest expansion values over a wider range of temperature compared with 90% linear low-density polyethylene/10% high-density polyethylene.
Lattice structures are regarded as excellent candidates for use in lightweight energy-absorbing applications, such as crash protection. In this paper we investigate the crushing behaviour, mechanical properties and energy absorption of lattices made by an additive manufacturing process. Two types of lattice were examined: body-centred-cubic (BCC) and a reinforced variant called BCC z . The lattices were subject to compressive loads in two orthogonal directions, allowing an assessment of their mechanical anisotropy to be made. We also examined functionally graded versions of these lattices, which featured a density gradient along one direction. The graded structures exhibited distinct crushing behaviour, with a sequential collapse of cellular layers preceding full densification. For the BCC z lattice, the graded structures were able to absorb around 114% more energy per unit volume than their non-graded counterparts before full densification, 1371 ± 9 kJ/m3 versus 640 ± 10 kJ/m3. This highlights the strong potential for functionally graded lattices to be used in energy-absorbing applications. Finally, we determined several of the Gibson–Ashby coefficients relating the mechanical properties of lattice structures to their density; these are crucial in establishing the constitutive models required for effective lattice design. These results improve the current understanding of additively manufactured lattices and will enable the design of sophisticated, functional, lightweight components in the future.
A thermosetting epoxy resin system consisting of diglycidylether of bisphenol A (DGEBA) and m-xylylenediamine (MXDA) was successfully foamed by carbon dioxide (CO2) using two-step batch process. Isothermal curing kinetics of epoxy system was developed to help control the pre-curing degree of resin under different pre-curing conditions. Samples with different pre-curing degrees were prepared and then foamed via temperature-rising foaming process. It was found that the pre-curing degree was a crucial index for the foamability of epoxy resin. The effects of pre-curing conditions on curing reaction as well as further foaming results were investigated, and the results showed that the pre-curing degree from 37.7% to 46.3% was the proper foaming range for the chosen epoxy resin. With increasing pre-curing degrees from 37.7% to 51.6%, viscosity and elasticity of pre-cured resins increased, and correspondingly, average cell size of epoxy foams decreased from 329.8 µm to 60.8 µm while cell density increased from 1.4 x 105 cells/cm3 to 8.6 x 105 cells/cm3. Furthermore, the foamed samples with the same pre-curing degree had similar cell morphology regardless of pre-curing conditions.
Thermoplastic polyurethane possesses many special characteristics. Its flexibility, rigidity, and elasticity can be adjusted by controlling the ratio of soft segments to hard segments. Due to its versatile physical properties, thermoplastic polyurethane is commonly used in transportation, construction, and biomaterials. However, methods for thermoplastic polyurethane foam production using CO2 are still under investigation. We have previously prepared nanoporous thermoplastic polyurethane foam using commercially available thermoplastic polyurethane; however, in this study, thermoplastic polyurethane was synthesized using 4,4'-methylenebis(phenyl isocyanate), poly(propylene glycol) and 1,4-butanediol, without solvents, using a pre-polymer method. The properties of the synthesized thermoplastic polyurethane were characterized by Fourier transform infrared spectroscopy, thermal analysis, and their mechanical properties were measured. The synthesized thermoplastic polyurethane was foamed by batch foaming using supercritical CO2 as the blowing agent. The effect of saturation temperature and saturation time on the cell morphology of the thermoplastic polyurethane foam was examined.
Rigid thiourethane foams were prepared from vegetable oil-based polythiols (polymercaptans) and compared with soy- and castor oil-based polyurethane reference foams. Three types of polymercaptans were tested, soybean oil-based one with thiol groups only, epoxidized soybean oil-based with vicinal thiol and hydroxyl groups and castor oil-based with hydroxyl and thiol groups separated with several methylene units. Physical, mechanical, and thermal characteristics of polyol- and thiol based foams were similar to petrochemical foams used as heat insulation materials in construction, appliances, etc.
Flame-retardant polybenzoxazine foams containing 1% phosphorus were prepared from diphenolic acid-based benzoxazine and 9,10-dihydro-9-oxa-10-(1-hydroxy-1-methylethyl)phosphaphenanthrene-10-oxide. Statistical predictive models were developed to determine the influence of the foaming time (tf) and foaming temperature (Tf) on the density, compressive modulus, and compressive strength of the foams. Results showed that the density of the foams exhibited great dependence on tf, whereas both compressive properties were more dependent on Tf and tf. Additionally, the flammability of the foams was also characterized by the limiting oxygen index. The presence of 9,10-dihydro-9-oxa-10-(1-hydroxy-1-methylethyl)phosphaphenanthrene-10-oxide greatly improved the flame retardancy of the resulting foams.
In this study, flame-retardant poly(lactic acid) foams with satisfactory cell structures were prepared by microcellular foaming technology using phosphorus-containing flame retardant and graphene as the charring agent. The introduction of 5–30 wt% flame retardant increased the limited oxygen index value of poly(lactic acid) from 19.0 to 26.5–37.8% and simultaneously increased the foam expansion of poly(lactic acid) foams from 4.4 to 5.8–17.5. In addition, all the prepared poly(lactic acid)/flame-retardant composites passed the UL-94 V-0 rating. The addition of 0.5 wt% graphene increased the limited oxygen index value of poly(lactic acid)/flame-retardant composite with flame-retardant content of 15 wt% from 27.9 to 29.2%, and more graphene additions improved the antidripping behavior of poly(lactic acid) composites. The possible mechanisms of the effects of the resultant cellular structure on the flame-retardant properties of poly(lactic acid) composites were also discussed.
Relationships for the prediction of various linear mechanical properties of polymeric sandwich foams obtained in injection processes were studied in comparison with shear, tensile, and flexural tests. The samples were obtained by a core-back foam injection molding process that enables one to obtain sandwich materials with dense skins and a foamed core as revealed by the morphological analysis. Tensile, shear, and flexural moduli were investigated for the skin, the core, and the overall foamed structure. In addition, the Poisson’s ratio of the skin was also determined. The core properties were specifically analyzed by machining the samples and removing the skins. Tensile and shear properties of the core can be well described by the Moore equation. The tensile modulus can be calculated by a linear mixing rule with the moduli of the skin and of the core in relation to the thickness of the layers. Shear and flexural moduli are described by a linear mixing rule on the rigidity in agreement with the mechanics of beams. Tensile modulus, out-of-plane shear modulus, and flexural modulus can finally be predicted by the knowledge of only very few data, namely the tensile modulus and Poisson’s ratio of the matrix, the void fraction, and thickness of the core. The equations were proved to be physically meaningful and consistent with each other.
In recent years, the mold-opening foam injection molding technology has received great attention as a breakthrough technology for the production of low density and open-cell foams of three-dimensional geometries. Despite the earlier studies, there has been little investigation on the control of the foaming temperature of this foam manufacturing process. To help understand the mechanisms behind this technology, this paper presents a numerical approach to simulate the cooling of the polymer/gas mixture inside the mold cavity, and thereby, estimating the foaming temperature of this manufacturing process. The temperature of the material inside the mold cavity prior to the mold-opening foam expansion process was mathematically modeled and resolved using finite difference approximation. Iteration considerations to the exothermic crystallization phenomenon for semi-crystalline polymers were also presented with reference to the non-isothermal crystallization characteristics from the differential scanning calorimetry (DSC) analysis. The numerically simulated results were shown to agree with the results obtained from a set of mold-opening foam injection molding experiments.
New polyols have been obtained in reactions of N,N,N’,N’-tetrakis(2-hydroxyethyl)-derivatives of oxamide, esterified with boric acid (BA), with the excess of ethylene carbonate (EC). The preparation conditions of polyols and next the production of polyurethane foams with the use of these new polyols have been presented. The foaming process parameters as well as the testing of the foam properties have been given. The structure modification of the polyurethane foams by means of oxamide and borate groups resulted in high thermal stability and thermal resistance, dimensional stability, compressive strength as well as the reduced flammability.
In order to decrease the cell size and maintain very high volume expansion ratio simultaneously, a methodology for the preparation of complex cellular structure (CCS) in polystyrene/poly(ethylene terephthalate glycol-modified) (PS/PETG) blend using two-step depressurization pressure batch foaming process was proposed. First, the optimum foaming temperature for PS and PS/PETG blend, respectively, were confirmed by one-step depressurization foaming process. Then, the CCS in PS and PS/PETG blending foam were fabricated by two-step depressurization foaming process at the optimum foaming temperature. The rheological properties of PS and PS/PETG blend were tested by dynamic rotational rheometer. The dispersion morphologies and foam morphologies were observed by scanning electron microscope. The lowest densities of PS and PS/PETG blending foams were obtained at the temperature of 136℃. The interfaces between PS and PETG could act as nucleation sites for the cell nucleation, which were helpful to fabricate the CCS. The CCS could be controlled by tuning the degree of the first-step depressurization and the holding time. The results showed that the large cells could be beneficial to decrease the foam density and the presence of small cells was beneficial to increase the cell number.
In this paper, we report the design of a new experimental apparatus for the study of the foaming process of thermoplastic polymers with physical blowing agents. The novel lab-scale batch foaming equipment is capable of achieving accurate control of the processing variables, namely, the temperature, the saturation pressure and the pressure drop rate and, furthermore, of allowing the achievement of very high pressure drop rates, the observation of the sample while foaming and the very fast extraction of the foamed sample. By recalling the considerations discussed by Muratani et al. (J Cell Plast 2005; 24: 15), the design converged into a simple, cheap, and very small pressure vessel, thereby denoted as mini-batch. We herein describe the overall design path of the mini-batch, its characteristics, configurations, together with some examples of use with polystyrene and CO2 as the blowing agent.
Nowadays, polyurethane foams play a key role in widespread applications, and their market demand is still growing globally. This work aims to prepare hydroxyl telechelic liquid natural rubber, a bio-based polyol, as a sustainable raw material and to enhance elastic properties of soft segment bio-based polyurethane foams. A hydroxyl telechelic liquid natural rubber with a viscosity-average molecular weight of 4.2 x 103 g/mol was successfully produced by oxidative degradation of natural rubber with hydrogen peroxide in the presence of supercritical carbon dioxide, then modifying the chain-end functionality to obtain hydroxyl number of 59 mg KOH/g. The functionality of hydroxyl telechelic liquid natural rubber was confirmed by FT-IR and 1H-NMR. Bio-based polyurethane foams were then prepared by mixing the synthesized hydroxyl telechelic liquid natural rubber with commercial diisocyanate. Morphological properties and thermal stability of polyurethane foams were investigated.
Foam core based sandwich composite materials are extensively used in marine sectors because of its high strength and stiffness to weight ratios. The structural materials used for marine applications should possess good damage tolerance capability. Hence, it is essential that these materials shall be tested for their residual mechanical properties when exposed to marine environment. In the present work, syntactic foam is prepared by uniform mixing of dry fly ash cenosphere and phenolic resin in equal proportions. Syntactic foam is further stiffened by integrating it with honeycomb structure during manufacturing. Sandwich composites are developed with core of syntactic foam (with and without honeycomb structure) and face skins of glass/epoxy composite. Sandwich coupons are prepared in two batches; one being subjected to ageing in natural sea water and other under accelerated environment. Both aged and unaged coupons are subjected to mechanical tests to determine their residual properties under compression, flexure, and low-velocity impact as per ASTM standards. Results showed that the moisture absorption is significant up to about 60 days beyond which it is marginal. The saturation level was attained for an immersion period of about one year, at which the material exhibited significant damage, at the interfacial regions of core-skin, cenosphere-phenolic resin, and fiber-matrix. Ageing of sandwich composites under sea water and accelerated environment has shown detrimental effect on their mechanical properties. However, the extent of degradation in properties due to ageing can be reduced by the incorporation of resin impregnated honeycomb structure in syntactic foam. Microscopic features of aged coupons are also investigated to predict mode of damage due to ageing.
Auxetic epoxy resin foams were produced by solid-state foaming thanks to the use of properly shaped precursors. In fact, a re-entrant hexagonal shape of the precursors is preserved during foaming and results in a foam with a complex structure: a thin macro-structure with the re-entrant geometry filled with foam. The auxetic behavior was observed by using tensile tests at different temperatures (room temperature, 80℃, and 100℃). Indentation tests were also carried out to evaluate the gradient properties across the lines of the thin re-entrant macro-structure. In order to show that the auxetic behavior depended on the internal macro-structure, tests were also performed on foam panels obtained by cylindrical tablets and, therefore, with a standard-hexagonal macro-structure. In conclusion, the auxetic behavior was observed only for the foam panels with re-entrant hexagonal structure at 80℃. In this case, a negative Poisson’s ratio is immediately achieved at small strains and tends to a zero plateau value for longitudinal strains up to 1%.
As a novel injection molding process, microcellular injection molding process has the characteristics of saving material, decreasing warpage and surface sink mark, improving dimensional accuracy, etc. But for the plastic part with thick reinforcing ribs, if selection of process parameters are not reasonable, foaming quality of melt will be affected and obvious sink mark defects will appear on the surface of plastic part. This paper selected a medical appliance shell with many reinforcing ribs as research object. Simulation experiments of microcellular injection molding process were performed by using orthogonal experiment method. The influence of different process parameters, such as mold cavity surface temperature, melt temperature, injection rate, cooling time, weight reduction ratio and supercritical fluid level, on the surface sink mark of microcellular injection molding part was studied by using signal-to-noise ratio analysis and analysis of variance . The results showed that mold cavity surface temperature was the most important influence factor on surface sink mark depth of microcellular injection molding part, followed by weight reduction ratio, cooling time, supercritical fluid level, injection rate and melt temperature. Meanwhile, the optimal combination of process parameters was obtained for minimizing sink mark depth of microcellular injection molding part. The average surface sink mark depth of microcellular injection molding part molded by using the optimized process parameters was only 2.62 µm, compared to 4.87 µm of average surface sink mark depth of microcellular injection molding part molded by using the process parameters before optimization, the average sink mark depth of microcellular injection molding part was reduced by 46.2%. Finally, the forming mechanism of sink mark of microcellular injection molding part at locations of reinforcing ribs was discussed, and the influence mechanism of different process parameters on surface sink mark defects of microcellular injection molding part was also analyzed.
The microcellular injection-molded part usually consists of a foamed core region and two unfoamed skin layers on the cross section. This paper investigated the formation process, formation mechanism and structural characteristics of the unfoamed skin layers in microcellular injection-molded part. It is found that the unfoamed skin layers are formed in two processes namely "during filling" process and "after filling" process. The shear flow and the fountain flow behaviors of the melt in the filling stage are the main controlling factors on the formation of the unfoamed skin layer in "during filling" process, and the cooling solidification of the melt in cooling stage is the fundamental reason for the formation of the unfoamed skin layer in "after filling" process. Further studies found that the unfoamed skin layer in microcellular injection-molded part has two distinct regions, the outer region is a thin frozen layer which contains deformed and broken cells, and the inner region is a relatively thick solid-like layer which has no visible cells in. The unfoamed skin layer has a minimum thickness in the gate location. The whole thickness of the unfoamed skin layer is decreased with the increase of injection speed and mold temperature, but is slightly affected by melt temperature.
The investigation of the influence of chemical blowing agent addition and talc filler on structure and selected properties (weight, thickness, mechanical properties, surface state – gloss and colour – and thermal conductivity) of moulded parts from PP was the aim of this work. Microscopic investigations were made using mould with cavities of variable height. Addition of blowing agents to polymer material permits reducing of the injection cycle to the injection phase and cooling. Investigations showed that talc addition permits to obtain fine-cellular structure in moulded parts with blowing agent. It is possible, because talc can act as a nucleating agent, which has been shown in literature. As a result, moulded parts with blowing agent and talc had low weight, good mechanical properties compared to solid, unfilled parts. Main disadvantage of using blowing agent and talc is worsening of gloss and colour changing.
In the first part of this study, asymmetric microcellular composites were prepared by injection molding to study their morphological properties as a function of temperature gradient inside the mold (0–60℃), as well as foaming agent (0–1%) and natural fiber (0–30%) contents. High-density polyethylene, flax fiber, and azodicarbonamide were used for the matrix, reinforcement, and chemical blowing agent, respectively. From the samples produced, mechanical properties (tensile, flexion, torsion, impact) are analyzed in this second part. Mechanical properties were found to be strongly influenced by density reduction and natural fiber content. It was also found that fiber addition provides higher reinforcement in flexion than torsion and tension. Also, flexural modulus and impact strength were relatively unaffected by foaming agent content for the range of parameters studied. From the experimental data obtained, a simple mechanical model based on density profile is presented to predict the elastic moduli of asymmetric structural composite foams.
This paper examines the feasibility of using polyols from vegetable oils as base polyols (i.e. with 50% or more in a blend with petrochemical polyols) for flexible molded polyurethane foams. A series of hyperbranched (HB) polyols were synthesized by transesterification of hydroxy fatty acid methyl esters and different modifiers to control viscosity, hydrophilicity, molecular weight, and functionality. All HB polyols had hydroxyl numbers around 85 mg KOH/g, with the exception of one which was 105 mg KOH/g. When mixed with petrochemical polyols with OH numbers 35 and 28 mg KOH/g, the HB polyols acted primarily as high molecular weight crosslinkers that increased the stiffness of the polymeric network and the load-bearing properties but decreased the tensile strength, elongation, and tear strength. However, most of the foams met the targeted tensile and tear strength values while some of the foam formulations provided satisfactory elongation. The best mechanical properties were obtained from foams with phthalic anhydride-modified HB polyols. It was demonstrated that flexible molded foams with satisfactory properties can be obtained with 50% and 65% of HB soy polyols in a blend with PPO polyols.
The effect of fibre length and fibre aspect ratio on the reinforcement of soybean-based polyurethane foams was investigated. Micro-crystalline cellulose fibres and 260-µm long glass fibres embedded inside polyurethane foams were studied separately. Using X-ray tomography, it was determined that short micro-crystalline cellulose fibres were found solely embedded within the cell struts of the polyurethane foam. The cell struts were reinforced by the micro-crystalline cellulose fibres based on composite theory. An attempt was made to predict the reinforcement by using existing micro-mechanical models including the rule of mixtures and shear-lag theory. The overall foam compressive modulus increased based on the reinforcement of the cell struts and correlated with the foam mechanics model developed by Gibson and Ashby. The intermediate length 260-µm long glass fibres were found to span cells in polyurethane foam and were not embedded within the cell struts. These glass fibres did not contact each other. The reinforcement performance of the intermediate length glass fibres was found to be worse than the short micro-crystalline cellulose fibres. Therefore, these intermediate length fibres that span cells should be avoided for use in reinforcement of soybean-based polyurethane foams.
Medium to low density thermoplastic nanofoams have previously been produced using nanoparticles as nucleating center. Here we show that by designing the molecular structure of the polymer matrix to achieve high CO2 solubility while controlling the glass transition temperature, it is possible to produce nanofoams with cell nucleation densities as high as 1016/cm3 without introducing nucleation aids. This was achieved by maximizing foam expansion without uncontrolled cell ripening for a series of acrylic copolymers, which were foamed under a set of standard conditions. To predict the role of foaming conditions on foam characteristics, a theoretical foaming model was built to simulate cell nucleation, growth and foam stabilization. Experimental or predicted properties of the polymer/carbon dioxide mixture were used as inputs. Despite simplifying assumptions, such as the use of classical nucleation equations, the semi-quantitative model provides insight into the foam expansion behavior and validates experimental observations.
Tissue engineering provides a novel and promising approach to replace damaged tissue with an artificial substitute. Porous synthetic biodegradable polymers are the preferred materials for this substitution due to their microstructure, biocompatibility, biodegradability, and low cost. As a crucial element in tissue engineering, a scaffold acts as an artificial extracellular matrix (ECM) and provides support for cell migration, differentiation, and reproduction. The fabrication of viable scaffolds, however, has been a challenge in both clinical and academic settings. Methods such as solvent casting/particle leaching, thermally induced phase separation (TIPS), electrospinning, gas foaming, and rapid prototyping (additive manufacturing) have been developed or introduced for scaffold fabrication. Each method has its own advantages and disadvantages. In this review, the commonly used synthetic polymer scaffold fabrication methods will be introduced and discussed in detail, and recent progress regarding scaffold fabrication—such as combining different scaffold fabrication methods, combining various materials, and improving current scaffold fabrication methods—will be reviewed as well.
Foams from engineering thermoplastics like poly(butylene terephthalate) (PBT) are a new generation of polymer foams and, probably, the future for lightweight, insulation and damping materials. By means of foam extrusion or bead foaming, it is possible to achieve low-to-medium density foams (< 500 kg/m3). However, foam extrusion of PBT is quite challenging due to its low melt strength and drawability combined with a small temperature-processing window, which is a characteristic of semi-crystalline thermoplastics. This work proves that the problem of cell coalescence and insufficient cell stabilisation can be reduced by choosing the right material and processing parameters in foam extrusion with underwater pelletizing. Therefore, expanded PBT beads could be realised for the first time using CO2 as supercritical blowing agent. To obtain spherical low-density PBT beads with a homogenous foam structure, different process parameters were systematically studied with two different commercial extrusion grades and different blowing agent concentrations. The influence of water pressure and cutting speed of the underwater pelletizer on foam morphology of E-PBT and bead structure was studied. It was shown that using a polymer grade with a sufficiently high-melt viscosity helps to reduce cell coalescence. The lowest achieved density was 230 kg/m3. An increase of the blowing agent concentration did not help in reducing the density. The melting range was investigated by differential scanning calorimetry and yielded reasonable moulding temperatures of 205–215 ℃. This corresponds to steam pressures of 17–21 bar in a steam-moulding machine.
Use of compression molding with a natural fiber-reinforced thermoplastic matrix has been growing rapidly within the last few years in various applications. Wood-reinforced high-density polyethylene offers economic efficiency, a high process reproducibility, short cycle times, a stable and high component quality, and a good recycling ability. In the present study, the distribution of fiber orientation using micro-CT scanner for compression-molded product of varying fiber content was measured, and the effects of fiber content with respect to orientation states are discussed.
Cushion foam sheets, made from different blends of wheat starch, were developed with a co-rotating twin-screw extruder machine and compared to commercial plastic foam cushions. An experimental study was developed to identify the effect of three ingredients: glycerol, gluten, and sodium bicarbonate on the bulk expansion, the cellular structure and the mechanical properties of the resulted foams. The experiments showed that the properties of the resulted foams were affected by the formulation. Foams with high level of glycerol and gluten content had lower densities and higher expansion ratio, cell size area, and cell wall thickness than blends with high level of sodium bicarbonate, which had better mechanical strength but less elasticity and shock absorption. The extruded materials had shown their suitability for cushioning use by having comparable physical properties with the commercial plastic foams. The dynamic cushion curve test indicated that the starch-based foam sheets provided good shock absorption properties. They had lower and larger deceleration peak than the expandable polyethylene foams we tested.
This paper reported a novel halogen-free flame retardant poly (vinyl alcohol) (PVA) foam with intrinsic flame retardant characteristics prepared through continuous extrusion using water as blowing agent. The morphology, cellular structure, mechanical properties and flame retardancy of the foams were systematically investigated. The experiments showed that PVA was not only the flame retardant target foam matrix, but also played an important role in char forming reactions, water not only acted as plasticizer and blowing agent for PVA thermal foaming, but also an effective synergistic flame retardant by evaporation to cool the system and suppress the point of inflammability, and melamine phosphate (MP) as halogen-free flame retardant was well dispersed in PVA matrix due to the strong interaction between MP and PVA, and also acted as excellent heterogeneous nucleating agent for foaming. The prepared halogen-free flame retardant PVA foam had good cellular structure, excellent flame retardancy and mechanical properties, i.e. apparent density 0.25 g/cm3, average cell diameter 450 μm, cell density 103 cells/cm3, reaching UL94 V-0, LOI 35%, tensile strength 1.8 MPa and elongation at break 57.1%. The novel halogen-free flame retardant PVA foam has potential applications.
Hybrid materials, a new class of materials obtained by sol-gel approach and based on the nanoscale interaction between inorganic and organic phases, have recently gained large scientific and industrial attention. In this work, the material designing of zein hybrid materials with tailored properties is addressed to the production of zein hybrid foams by both gas foaming and supercritical carbon dioxide, CO2 drying. Hybrid materials have been produced from thermoplastic zein and 3-glycidoxypropyltrimethoxysilane by a two-step procedure including reactive melt mixing and a simultaneous sol-gel approach. Protein structural changes have been investigated by infrared spectroscopy and correlated with thermomechanical properties. The hybrid foams have been analyzed by scanning electron microscopy in order to evaluate the effect of silsesquioxanes domains on the porous structure. Hybrid microcellular foams with homogeneous cellular structures have been obtained by both foaming approaches. A bimodal structure with bubbles characterized by micrometric and nanometric sizes was obtained in hybrid foams obtained with CO2 drying.
Microcellular injection molding of polypropylene and glass fiber composites (PP-1684/GF-950) was performed using supercritical nitrogen as the physical blowing agent. Based on design of experiment matrices, the influences of glass fiber content and operating conditions on cell structure, glass fiber orientation and mechanical properties of molded samples were studied systematically. The results showed the cell morphology and glass fiber orientation of foaming parts were definitely influenced by the cooling and shear effects. The mechanical properties of foamed polypropylene–glass fiber composites could be effectively enhanced by improving the cell morphology, dispersion state and orientation of the glass fiber at optimal weight percentage
Asymmetric microcellular composites were prepared by injection molding to study the effects of temperature gradient inside the mold (0 to 60℃) as well as blowing agent (0 to 1%) and natural fibers (0 to 30%) contents. High-density polyethylene, flax fiber, and azodicarbonamide were used as the matrix, reinforcement, and chemical blowing agent, respectively. From the samples produced, a complete morphological characterization was performed. As expected, cell size, cell density, and skin and core thicknesses were affected by blowing agent and natural fiber contents and mold temperatures. It was found that a better microcellular asymmetric structure was obtained with higher fiber and blowing agent contents and higher average mold temperature. From the data obtained, a simple mathematical model was used to fit the relative density of asymmetric foams to include skin, core, and transition zone thicknesses.
New polystyrene (PS)/carbon nanofiber (CNF) and PS/graphite foams with an inter-connected honeycomb-like carbon particulate network of CNF or graphite were prepared by first coating the surface of polymer pellets with either CNF or graphite and then conducting batch foaming using carbon dioxide (CO2) as a blowing agent. It was found that the inter-connected honeycomb-like carbon particulate network could significantly reduce the compression yielding of conventional PS foams. With 1 wt% of CNFs or graphite, the PS foams with inter-connected honeycomb-like carbon particulate network were 5–9 times more electrically conductive than foams made of compounded PS nanocomposite with the same carbon particle loading. In addition, the PS foams with inter-connected honeycomb-like carbon particulate network were more thermally conductive and revealed significantly improved thermal stability comparing to foams made of compounded polymer nanocomposites.
The method of synthesis of oligoetherols with purine ring and boron was presented based on reaction of hydroxyethyl derivative of uric acid with boric acid and alkylene carbonates. Their physical properties and structure were established. The obtained oligoetherols were suitable reactants to obtain polyurethane foams. The foams were further obtained and characterized by measuring their apparent density, water uptake, linear dimension changes, and heat conductance. It has been found that polyurethane foams have enhanced thermal resistance, diminished flammability, and better mechanical properties than polyurethane foams obtained from oligoetherols synthesized from uric acid and alkylene carbonates. The flaming rate of polyurethane foams with purine ring and boron was lower in comparison with foams with purine ring only (6.2–6.5 mm/s) and in case of the best compositions, i.e. those with high thermal resistance and appropriate compression strength it was as low as 0.86–1.25 mm/s.
A complex medical instrument exterior shell was chosen as a studying object to investigate the influence of relative low (<10 MPa) gas counter pressure process on microcellular injection molding process. The gas counter pressure microcellular injection mould and related experiments were designed. The relative low gas counter pressure under which the melt can foam was mainly considered to improve the surface quality of molded parts without significantly prolonging production cycle. The effects of the gas counter pressure parameters on the surface quality, cell morphology, and cell density of microcellular parts were studied. A critical melt flow front pressure to effectively eliminate surface swirl marks of microcellular injection molded part was proposed. The mechanism of the influence of gas counter pressure process on foaming behavior of melt in filling process was analyzed. The reasonable gas counter pressure parameters to improve surface quality of products without significantly increasing molding cycle were obtained. By using the obtained reasonable gas counter pressure parameters, a sound microcellular injection molded product was injected finally.
Bi-modal PS foams with various volume fractions of large cells (fL ), cell sizes and densities were prepared to investigate the effect of cell structures on the tensile and impact behaviors. The tensile results showed that for the similar density, the tensile strength and modulus decreased with the increase of fL , unless the cell size of large ones is smaller than 25 µm. Similarly, the impact experimental results showed that the impact strength decreased with increasing fL , unless the fL is in the range of 25–32%. It indicated that the bi-modal cell structure could lead to the better properties than that of uniform one, when the cell morphology was proper (fL in the range of 25–32% and the cell size of large ones smaller than 25 µm). The SEM images of impact-fractured surface of bi-modal foams further confirmed that the cell morphology with fL of 32% was more favorable to the absorption of impact energy during the fracture process.
Novel blended scaffolds combining biobased polylactic acid (PLA) and thermoplastic polyurethane (TPU) were fabricated by thermally induced phase separation (TIPS) using two different solvents. Pure PLA and TPU polymer scaffolds using 1,4-dioxane as the sole solvent exhibited typical ladder-like structures, while blended PLA/TPU scaffolds using the same solvent showed a more uniform microstructure. When de-ionized water was added to the solution as a non-solvent, scaffolds with the mixed solvent showed more open cells and greater interconnectivity. In compression tests, it was found that specimens, including pure PLA, TPU, and blended scaffolds with the mixed solvent, showed a higher compressive modulus than their counterparts that used dioxane as the single solvent. Dynamic mechanical analysis (DMA) was employed to characterize the shape memory properties of the scaffolds. DMA indicated that the shape fixing ratio was highest in the PLA scaffolds, while the shape recovery ratio of the TPU scaffolds was the greatest among the specimens. More interestingly, when the mixed solvent was used, the shape memory property of the blended scaffolds displayed a similar deformation curve to the TPU scaffold. This was due to the presence of the TPU phase and similarity in structure between PLA/TPU and TPU scaffolds when mixed solvent was used. In the degradation test, the blended scaffolds showed a balanced degradation behavior in-between the more easily degraded PLA and the more stable TPU in the phosphate-buffered saline (PBS), and the addition of water to the systems accelerated the degradation process of the specimens. Cell culture results showed that all of the scaffolds had good biocompatibility.
The expanded polypropylene beads with microcellular structure were prepared by an autoclave-based batch foaming process using non-supercritical CO2 as the foaming agent. Herein, smaller polypropylene micropellets (~0.6 mm) were obtained from three kinds of polypropylene resin by underwater micro-pelletizer system. The results from differential scanning calorimetry indicated that the double melting peaks of beads moved to higher temperature with increasing saturation temperature and pressure. The kind of comonomer did not exert noticeable influence on the double melting behaviors. The X-ray diffraction of expanded polypropylene bead revealed that characteristic peaks of α-type crystal did not change compared with that of original polypropylene micropellets. The relationship between cell morphology and saturation temperature/pressure of expanded polypropylene beads are discussed preliminarily by scanning electron microscope.
In this study, numerical approach for simulation of mold filling is presented. Polyurethane foam formation includes several complex phenomena such as chemical reactions, heat generation and blowing agent evaporation. Foam properties are variable during formation, foam viscosity increases and conductivity reduces. Foam phase is considered compressible and two phases are immiscible. Foam front will be captured by volume of fluid and appropriate governing equations will be implemented in OpenFOAM. This study prepares a numerical model to reduce several experimental runs with expensive prototypes for mold design.
Thermally insulating extruded polystyrene foams are currently produced with hydrofluorocarbon blowing agents. Hydrofluorocarbons have zero ozone depletion potential but rather high greenhouse warming potential. Various unsaturated fluoropropenes, with greenhouse warming potential values <15, have been assessed as HFC-134a replacements for styrenic extrusion foaming. The screening is first based on the modeling of solubility and diffusivity properties, followed by foaming experiments with a conventional extrusion process. Some fluoropropenes appear to be excellent blowing agents for extruded polystyrene foams and can be used alone for making very low-density foams with regular and large cell sizes, while some others require the use of a co-blowing agent for processing good quality foam. A few others are not suitable as a blowing agent for extruded polystyrene foams due to their toxicity or their very poor transport properties.
This work is aimed at investigating the crystallization behavior of solid and microcellular injection molded polypropylene/nano-calcium carbonate composites. The effects of processing conditions, such as injection speed, mold temperature, and carbon dioxide concentration (used in microcellular injection molding), as well as the filler concentration on the crystal form, crystal orientation, and crystallinity were studied using 2D-wide-angle X-ray diffraction and differential scanning calorimetry. β-form crystals found in the surface layer of injection molded samples under high injection and mold temperature due to stronger shear effect. The orientation degree calculated from the X-ray diffraction images by the Hermans function was high in the surface layer and decreased as the distance from the mold surface increased. The addition of the nano-calcium carbonate filler promoted the formation of β-form crystals but reduced the orientation degree and crystallinity as the nanoparticles disturbed the orientation of the molecular chains. On the other hand, when using the foaming process, the formation of β-form crystals was inhibited and the orientation degree was reduced, but the crystallinity of the samples increased, likely due to enhanced molecular chain mobility from the supercritical carbon dioxide which acted as a plasticizer. The crystallinity of the samples was greater in the surface layer but showed no dependence on the injection speed or mold temperature.
Thermoplastic polyurethane is a commonly used polymer in our daily lives. Microcellular injection molding (a.k.a. MuCell) is an emerging method capable of mass-producing thermoplastic polyurethane foams with tunable microstructures and properties. This study investigated the effects of four main processing parameters—namely, plasticizing temperature, carbon dioxide (CO2) content, injection volume, and injection speed—on microcellular injection molded thermoplastic polyurethane ASTM tensile test bars. Property variables of interest included the cell diameter, cell density, skin layer thickness, and Young’s modulus. Influence sequences of parameters on each variable were obtained via the orthogonal array test method. It was found that the CO2 content primarily affected the cell diameter and cell density, whereas the temperature mainly influenced the skin layer thickness and Young’s modulus. Surface fitting of each dependent variable was done by combining its two most influential parameters from the experiment data. The value of each property variable within the processing window could then be predicted from the fitted surface. In addition, microcellular injection molding of thermoplastic polyurethane was simulated by a commercial software package, and the simulated results confirmed the reliability of the cell diameter prediction.